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EP0792891A1 - Procédé de préparation d'un latex à base de diènes conjugués par polymérisation en emulsion - Google Patents

Procédé de préparation d'un latex à base de diènes conjugués par polymérisation en emulsion Download PDF

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Publication number
EP0792891A1
EP0792891A1 EP97102540A EP97102540A EP0792891A1 EP 0792891 A1 EP0792891 A1 EP 0792891A1 EP 97102540 A EP97102540 A EP 97102540A EP 97102540 A EP97102540 A EP 97102540A EP 0792891 A1 EP0792891 A1 EP 0792891A1
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Prior art keywords
monomers
latex
polymerization
particle size
weight
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EP97102540A
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German (de)
English (en)
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EP0792891B1 (fr
Inventor
Hans-Günter Dr. Vogt
Heinrich Dr. Grave
Hermann-Josef Bross
Martin Dr. Matner
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Polymer Latex GmbH and Co KG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated

Definitions

  • the present invention relates to a method for producing latexes based on conjugated dienes by means of emulsion polymerization.
  • the latices produced by the process according to the invention are particularly suitable for producing diving articles, such as gloves, synthetic leather, and coatings, such as carpet backing, paper coating and leather coating.
  • Batch processes generally have the disadvantage that, for example, slight deviations in the temperature or the starting materials from the target quantities lead to significant fluctuations in the number of particles, which in turn has a strong influence on the rate of polymerization.
  • Infeed processes have advantages over batch processes in terms of production safety, since only a part of the total amount of monomers is present during the polymerization. Compared to the batch process, however, more crosslinked polymers result in homo- or copolymers of conjugated dienes, which is disadvantageous for certain applications.
  • the object of the present invention is therefore to provide a method which avoids the disadvantages of the batch method described above and the disadvantages of the feed method described above.
  • latices are to be produced which, for example, have a low degree of branching and / or crosslinking and a high elongation at break.
  • the method according to the invention should have a high reproducibility and the formation of by-products (such as Diels-Alder products) should be minimized.
  • vinyl groups containing vinyl groups can be used in the process according to the invention as further monomers which can be copolymerized with the conjugated dienes mentioned above.
  • suitable vinyl group-containing compounds are: acrylonitrile, methacrylonitrile, dichlorobutadiene, ⁇ -methylstyrene, styrene, acrylic acid esters, methacrylic acid esters, vinyl carboxylic acids, such as methacrylic acid, Acrylic acid, fumaric acid and itaconic acid as well as methacrylamide and / or acrylamide.
  • vinyl compounds with N-methylolamide groups and / or with their ester or ether derivatives can be used as monomers.
  • the following are mentioned: N-methylolacrylamide, N-methylolmethacrylamide, N-methoxymethyl (meth) acrylamide, N-n-butoxy-methyl- (meth) acrylamide and / or N-acetoxymethyl (meth) acrylamide.
  • those with a sulfonic acid and / or a sulfonate group can be used as vinyl compounds.
  • the process of the invention it is possible to prepare both homopolymers based on the conjugated dienes mentioned and copolymers based on the conjugated dienes mentioned with the above-mentioned comonomers capable of copolymerization.
  • the proportion of the conjugated dienes in the copolymers is usually ⁇ 15% by weight, preferably 20 to 99% by weight.
  • the proportion of the comonomers containing vinyl groups is usually 85 85% by weight, preferably 80 to 1% by weight.
  • the quantitative ratio of the monomers used to one another depends on the particular intended use of the latices to be produced.
  • the optimal quantitative ratio of the monomers to one another can easily be determined by appropriate preliminary tests and e.g. according to the information in EP-A 0 442 370, p.4, lines 13-26.
  • Suitable seeds according to the invention are, for example, latices based on the latices to be produced by the process according to the invention, and also latices which are based on monomers other than the latices to be produced.
  • latices based on styrene and / or acrylonitrile and / or methyl methacrylate and / or butadiene and / or one of the vinylcarboxylic acids already mentioned are suitable.
  • seed latices homopolymer latices based on styrene or butadiene, carboxylated copolymer latices based on styrene or methyl methacrylate as main monomers and on the aforementioned vinyl carboxylic acids as comonomers.
  • the particle size of the seeds presented is in the range from 10 to 80 nm, preferably in the range from 20 to 50 nm.
  • Inorganic pigments whose particles can act as seeds for further polymerization can also be used as seeds for the process according to the invention.
  • pigments with an average particle size of 5 to 100 nm are suitable, such as silica sol, the use of which as a seed for emulsion polymerization has been described in the literature (Hergeth, Rigre, Schmutzler, Wartewig, Polymer, 1988, Vol. 29, 1923-8; Furusawa, Kimura, Tagawa, J. Colloid Interface Sci., 1986, 109 (1), 69-76).
  • the total amount of the seeds to be used can be presented or only a corresponding partial amount of the total seeds to be used.
  • the remaining amount of the seeds can then be added in the course of the polymerization.
  • the total amount of the seed is preferably introduced into the monomers to be polymerized.
  • the amount of seed to be used depends on the size of the latex to be produced and can be determined from equation (I) given above. It is usually 0.01 to 15, preferably 0.1 to 5% by weight. based on the total amount of monomers, with a particle size of 10 to 80 nm.
  • the ratio of the rate of polymerization of the monomers to the rate of addition of the monomers is less than 0.7: 1, preferably 0.05 to 0.7: 1, in particular 0.05 to 0.6: 1 .
  • the polymerization of the monomers used is carried out by the process according to the invention in the presence of a radical-forming activator, an emulsifier and in the presence of water.
  • Free radical-forming activators which can be used in the process according to the invention are, for example, inorganic peroxo compounds, such as hydrogen peroxide, sodium, potassium and ammonium peroxodisulfate, peroxocarbonates and borate peroxide hydrates, furthermore organic peroxo compounds, such as acyl hydroperoxides, diacyl peroxides, alkyl hydroperoxides and dialkyl peroxides, and also esters .-Butyl perbenzoate, as well as combinations of inorganic and organic activators.
  • the amounts of activator are usually in the range from 0.01 to 5% by weight, based on the total amount of the monomers used, preferably in the range from 0.05 to 2.0% by weight.
  • the inorganic and organic peroxo compounds (activators) mentioned can also be used in a known manner in combination with one or more suitable reducing agents.
  • suitable reducing agents are: sulfur dioxide, alkali disulfites, alkali and ammonium hydrogen sulfites, thiosulfate, dithionite and formaldehyde sulfoxylates, also hydroxylamine hydrochloride, hydrazine sulfate, iron (II) sulfate, glucose and ascorbic acid.
  • the amount of reducing agent is 0.01 to 1.0 wt .-%, based on the total monomer content.
  • the most suitable activator can be determined by appropriate preliminary tests. This depends in particular on the type of monomers used and on the reaction temperature of the polymerization.
  • buffer substances alkali metal phosphates and pyrophosphates (buffer substances) and, as chelating agents, the alkali metal salts of ethylenediaminetetraacetic acid (EDTA).
  • EDTA ethylenediaminetetraacetic acid
  • the amount of buffer substances and chelating agent is usually 0.01 to 1% by weight, based on the total amount of monomers.
  • chain transfer agents are often used for emulsion polymerization.
  • organic sulfur compounds such as C 1 -C 15 alkyl mercaptans
  • n-, i- and t-dodecyl mercaptan are preferred.
  • the amount of the chain transfer agent is usually 0.05 to 3% by weight, preferably 0.2 to 2.0% by weight, based on the total weight of the monomers used.
  • the dosage of the required stabilizer and / or the emulsifier is controlled so that the final particle size of the finished latex results from the equation given above.
  • the emulsifiers are known and are used in a conventional manner in emulsion polymerization (DC Blackley, Emulsion Polymerization, Chapter 7, Applied Science Publishers LTD, London, 1975).
  • emulsifiers to be used according to the invention So-called anionogenic emulsifiers, such as higher fatty alcohol sulfates, higher alkyl sulfonates, alkylarylsulfonates, aryl sulfonates and their condensation products with formaldehyde, salts of sulfosuccinic acid esters and sulfated ethylene oxide adducts.
  • anionogenic emulsifiers such as higher fatty alcohol sulfates, higher alkyl sulfonates, alkylarylsulfonates, aryl sulfonates and their condensation products with formaldehyde, salts of sulfosuccinic acid esters and sulfated ethylene oxide adducts.
  • non-ionic emulsifiers such as the known reaction products of ethylene oxide with fatty alcohols, such as lauryl, myristyl, cetyl, stearyl and oleyl alcohol, with fatty acids, such as lauric, myristic, palmitic, stearic and oleic acid, and their amides, and with alkylphenols, such as Isoctyl, isononyl and dodecylphenol.
  • the salts of fatty acids and resin acids are particularly suitable for the polymerization in the alkaline pH range.
  • the emulsifiers mentioned are generally used in amounts of 0.1 to 10% by weight, in particular 0.2 to 8% by weight, based on the total amount of the monomers used.
  • the total amount of the emulsifier to be used is such that the latex is stabilized during the polymerization in such a way that no coagulum is formed.
  • the emulsifier must not be added in too large an amount and also not at an early stage, since otherwise new latex particles are formed, which leads to an uncontrolled increase in the rate of polymerization.
  • the amount of water to be used in the emulsion polymerization is usually such that a solids concentration of the latex in water of 40 to 55% by weight results.
  • the process according to the invention is particularly suitable for the production of acrylonitrile-butadiene copolymer latices.
  • 15 to are preferred as monomers 60% by weight of acrylonitrile and / or methacrylonitrile, 39 to 84% by weight of butadiene, 0 to 10% by weight of one of the vinylcarboxylic acids mentioned and 0 to 25% by weight of an acrylic and / or methacrylic acid ester and / or styrene and 0 to 15% by weight of a vinyl compound with a sulfonate, amide, N-methylolamide and / or etherified and / or esterified N-methylolamide group.
  • the acrylonitrile-butadiene copolymer latices are prepared in the presence of a redox activator based on peroxo compounds with suitable reducing agents.
  • Redox activators based on hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide or t-butyl hydroperoxide in combination with alkali formaldehyde sulfoxylate or alkali disulfite as reducing agents, are particularly suitable for this.
  • the polymerization is preferably carried out in the presence of small amounts (0.0001 to 0.1% by weight, based on the total amount of monomers used) of Fe-II salts, optionally with the addition (up to 0.5% by weight) of a complexing agent , such as EDTA.
  • a complexing agent such as EDTA.
  • the polymerization For the production of the acrylonitrile-butadiene copolymer latices, it has proven to be advantageous to carry out the polymerization first up to a conversion of the monomers of up to 60%, preferably up to 70%, at temperatures from 10 to 60 ° C. then at a temperature 10 to 20 ° C higher (based on the temperature selected in section 1) (up to a maximum of 80 ° C) to a conversion of ⁇ 95%, preferably ⁇ 98%.
  • one or more emulsifiers are added in such a way that the growing latex particles are kept stable and the final particle size results from equation (I).
  • Acrylonitrile-butadiene copolymer latices with particle sizes in the range from 80 to 200 nm are preferably produced in accordance with the process of the invention.
  • the total amount of emulsifiers to be used is chosen so that no coagulum is formed during the polymerization.
  • 1 to 8% by weight of emulsifiers, based on the total amount of monomers used, are required.
  • the process according to the invention has the following advantage: it is a virtually coagulate-free polymerization with excellent reproducibility of the particle size and the rate of polymerization even with critical monomer compositions, the polymerization of which is conventional the technology is difficult to control and difficult to reproduce.
  • This includes, for example, the polymerization of acrylonitrile-butadiene copolymer latices with an acrylonitrile content> 40% by weight.
  • the latices produced according to the invention are distinguished by a lower content of undesired Diels-Alder by-products compared to latices produced in a batch process with conjugated dienes.
  • the latices based on conjugated dienes produced by the process according to the invention are used in particular in the manufacture of diving articles and synthetic leather base materials for binding fibers of all kinds and in the coating of paper, leather, textiles, nonwovens or carpet backing.
  • the particle sizes given in the examples were determined by laser correlation spectroscopy.
  • a particle size distribution was also recorded with the ultracentrifuge and the number-average particle size (TGs) was determined to be 37 nm.
  • the density of the particles of the seed used in the seed latex was 1.06 g / cm in all examples
  • 40 g of a 30% seed latex (particle size 37 nm) are heated in a nitrogen-purged autoclave with 302 g water to 80 ° C and for this a monomer / regulator mixture consisting of 368 g styrene, 600 g butadiene, 20 g acrylic acid and 10 g t-DDM (tertiary dodecyl mercaptan) metered in within 2 h.
  • an emulsifier feed consisting of 8 g of sodium dodecylbenzenesulfonate, 1 g of caustic soda, 1 g of ammonium persulfate and 450 g of water is metered in over the course of 2 hours.
  • an 8-hour activator feed consisting of 3 g ammonium persulfate and 60 g water is started.
  • the temperature was 80 ° C. throughout the polymerization.
  • the concentration determined by evaporation was 54.4%, corresponding to a conversion of 98.9%.
  • the ratio between the rate of polymerization and the rate of addition of the monomers was 0.25: 1.
  • the particle size was determined to be 163 nm (calculated 167 nm).
  • 40 g of a 30% seed latex (particle size 37 nm) are heated in a nitrogen-purged autoclave with 302 g water to 80 ° C and for this a monomer / regulator mixture consisting of 368 g styrene, 600 g butadiene, 20 g acrylic acid and 10 g t-DDM metered in within 12 h.
  • an emulsifier feed consisting of 8 g of sodium dodecylbenzenesulfonate, 1 g of caustic soda, 1 g of ammonium persulfate and 510 g of water is metered in over the course of 12 hours.
  • the temperature was 80 ° C. throughout the polymerization. After a total polymerization time of 18 h, the concentration determined by evaporation was 54.6%, corresponding to a conversion of 99.2%.
  • the ratio between the rate of polymerization and the rate of addition of the monomers was 0.80: 1.
  • the particle size was determined to be 169 nm (calculated 167 nm).
  • 67 g of a 30% seed latex are in a nitrogen-purged autoclave with 853 g of water, 0.5 g of tetrasodium ethylenediaminetetraacetate (Na 4 EDTA), 0.05 g of Na-formaldehyde sulfoxylate and 0.05 g of iron II-sulfate heated from 40 ° C, 1.0 g of t-butyl hydroperoxide added and a monomer / regulator mixture consisting of 450 g of acrylonitrile, 480 g of butadiene, 40 g of methacrylic acid and 5 g of T-DDM metered in within 3 h.
  • the emulsifier / activator mixture consisting of 30 g sodium lauryl sulfate, 0.5 g Na formaldehyde sulfoxylate and 280 g water is metered in over the course of 5 hours. After a total polymerization time of 15 h at 40 ° C., the concentration determined by evaporation was 46.3%, corresponding to a conversion of 99.4%.
  • the ratio between the rate of polymerization and the rate of addition of the monomers was 0.22: 1.
  • the particle size was determined to be 134 nm (calculated 138 nm).
  • 67 g of a 30% seed latex are in a nitrogen-purged autoclave with 853 g of water, 0.5 g of Na 4 EDTA, 0.05 g of Na-formaldehyde sulfoxylate and 0.05 g of iron-II-sulfate heated to 40 ° C., 1.0 g of t-butyl hydroperoxide were added and a monomer / regulator mixture consisting of 450 g of acrylonitrile, 480 g of butadiene, 40 g of methacrylic acid and 5 g of t-DDM were metered in over the course of 12 hours.
  • an emulsifier / activator mixture consisting of 30 g sodium lauryl sulfate, 0.5 g Na formaldehyde sulfoxylate and 280 g water is metered in over the course of 12 hours. After a total polymerization time of 15 h at 40 ° C, the concentration determined by evaporation was 46.1%, corresponding to a conversion of 98.9%.
  • the ratio between the rate of polymerization and the rate of addition of the monomers was 0.81: 1.
  • the particle size was determined to be 145 nm (calculated 138 nm).
  • 950 g of water, 7.5 g of sodium lauryl sulfate, 0.5 g of Na 4 EDTA together with a monomer / regulator mixture consisting of 450 g of acrylonitrile, 510 g of butadiene, 40 g of methacrylic acid and 5 g of t-DDM are dissolved in an autoclave flushed with nitrogen 40 ° C heated. It is activated with a solution of 0.05 g Na formaldehyde sulfoxylate, 0.05 g iron II sulfate in 50 g water and by adding 1.0 g t-butyl hydroperoxide and polymerized at 40 ° C. At a solids content of 15% and 30% determined by evaporation, a solution of 11.25 g sodium lauryl sulfate, 0.125 g Na formaldehyde sulfoxylate in 90 g water is added in each case.
  • Example 2 Comparison of the polymer properties of Example 2 with Comparative Examples 2a, 2b and 2c :
  • Example 2 describes the production according to the invention of an acrylonitrile-butadiene copolymer latex with 45% by weight of acrylonitrile and can be compared using a feed process according to the prior art (comparative example 2a) and a conventional batch process (comparative example 2b, c).
  • the Defo hardness for these latices was determined as a measure of the plastic deformability of the latices. Despite almost identical defo values, they are The tensile strength, the elongation at break and the tear propagation strength of the vulcanized films of the polymer from Example 2 are superior to Comparative Example 2a.
  • Comparative Example 2a Comparative Example 2a.
  • Comparative Example 2b the same level of values is achieved, however the disadvantages of poor reproducibility in the course of the polymerization and in the particle size of the final latex of comparative example 2b, c are avoided.
  • Example 3 and Comparative Examples 3a and 3b compared to Examples 2, 2a and 2b, the amount of regulator used for the polymerization was increased from 0.5 to 1.0% by weight, based on the monomers used.
  • 67 g of a 30% seed latex are in a nitrogen-purged autoclave with 853 g of water, 0.5 g of Na 4 EDTA, 0.05 g of Na-formaldehyde sulfoxylate and 0.05 g of iron-II-sulfate heated to 40 ° C., 1.0 g of t-butyl hydroperoxide were added and a monomer / regulator mixture consisting of 450 g of acrylonitrile, 480 g of butadiene, 40 g of methacrylic acid and 10 g of t-DDM were metered in over the course of 3 hours.
  • an emulsifier / activator mixture consisting of 30 g sodium lauryl sulfate, 0.5 g Na formaldehyde sulfoxylate and 280 g water is metered in over the course of 5 hours. After a total polymerization time of 15 h at 40 ° C., the concentration determined by evaporation was 46.4%, corresponding to a conversion of 99.4%.
  • the ratio between the rate of polymerization and the rate of addition of the monomers was 0.20: 1.
  • the particle size was determined to be 136 nm (calculated 138 nm).
  • 67 g of a 30% seed latex are in a nitrogen-purged autoclave with 853 g of water, 0.5 g of Na 4 EDTA, 0.05 g of Na-formaldehyde sulfoxylate and 0.05 g of iron-II-sulfate heated from 40 ° C, 1.0 g of t-butyl hydroperoxide added and a monomer / regulator mixture consisting of 450 g of acrylonitrile, 480 g of butadiene, 40 g of methacrylic acid and 10 g of t-DDM were metered in over the course of 12 h.
  • an emulsifier / activator mixture consisting of 30 g sodium lauryl sulfate, 0.5 g Na formaldehyde sulfoxylate and 280 g water metered in within 12 h. After a total polymerization time of 15 h at 40 ° C., the concentration determined by evaporation was 46.0%, corresponding to a conversion of 98.2%.
  • the ratio between the rate of polymerization and the rate of addition of the monomers was 0.81: 1.
  • the particle size was determined to be 138 nm (calculated 138 nm).
  • 950 g of water, 7.5 g of sodium lauryl sulfate, 0.5 g of Na 4 EDTA together with a monomer / regulator mixture consisting of 450 g of acrylonitrile, 510 g of butadiene, 40 g of methacrylic acid and 10 g of t-DDM are placed in an autoclave flushed with nitrogen heated to 40 ° C. It is activated with a solution of 0.05 g Na formaldehyde sulfoxylate, 0.05 g iron II sulfate in 50 g water and by adding 1.0 g t-butyl hydroperoxide and polymerized at 40 ° C. At a solids content of 15% and 30% determined by evaporation, a solution of 11.25 g sodium lauryl sulfate, 0.125 g Na formaldehyde sulfoxylate in 90 g water is added in each case.
  • the polymerization was not controllable in the conversion range between 50 and 70%, so that an uncontrolled rise in temperature from 40 ° C. to 55 ° C. was observed.
  • the polymerization was complete after 7 hours.
  • the concentration of the latex was 46.7%, corresponding to a conversion of 99.5%.
  • the particle size was only 86 nm.
  • Comparative example 3b carried out by the batch process, shows that the polymerization cannot be controlled in this process.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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EP97102540A 1996-02-29 1997-02-17 Procédé de préparation d'un latex à base de diènes conjugués par polymérisation en emulsion Expired - Lifetime EP0792891B1 (fr)

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DE19607631 1996-02-29
DE19607631 1996-02-29

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EP0792891B1 EP0792891B1 (fr) 1999-08-11

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US (1) US5750618A (fr)
EP (1) EP0792891B1 (fr)
JP (1) JP4478217B2 (fr)
CA (1) CA2198447C (fr)
DE (2) DE19649331A1 (fr)
ES (1) ES2137031T3 (fr)

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WO2008034813A1 (fr) * 2006-09-20 2008-03-27 Basf Se Particules contenant un additif polymère
EP1198509B2 (fr) † 1999-07-26 2009-04-08 Bangkok Synthetics Co. Ltd. Compositions adaptees a la fabrication d'articles manufactures elastomeres
WO2017164726A1 (fr) 2016-03-21 2017-09-28 Synthomer Sdn. Bhd. Latex polymère pour des applications de moulage par immersion
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WO2017209596A1 (fr) 2016-06-01 2017-12-07 Synthomer Sdn. Bhd. Latex polymère destiné aux applications de moulage par immersion
WO2018111087A1 (fr) 2016-12-15 2018-06-21 Synthomer Sdn. Bhd. Compositions de latex polymère durcissable pour la fabrication d'articles en caoutchouc
WO2021029763A1 (fr) 2019-08-09 2021-02-18 Synthomer Sdn. Bhd. Composition de latex polymère pour la préparation d'un film élastomère ayant des propriétés autorégénérantes
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WO2022216149A1 (fr) 2021-04-07 2022-10-13 Synthomer Sdn Bhd Composition de latex de polymère
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WO2024107042A1 (fr) 2022-11-15 2024-05-23 Synthomer Sdn Bhd Composé de silane et compositions le contenant
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KR100384375B1 (ko) * 1998-08-18 2003-08-21 주식회사 엘지화학 대구경 고무 라텍스 제조 방법
MY125326A (en) * 1999-06-21 2006-07-31 Nippon A&L Inc A latex compound for dip molding and a dip-molded product
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CA2387816A1 (fr) 1999-10-20 2001-04-26 Basf Aktiengesellschaft Procede de production d'une dispersion aqueuse de particules constituees d'un polymerisat et d'un solide en fines particules anorganique
KR100335641B1 (ko) * 2000-02-21 2002-05-08 강석주 고속 인쇄용 도공지에 사용되는 고 접착력 라텍스의제조방법
US6870019B2 (en) * 2000-12-12 2005-03-22 Nippon A & L Inc. Latex for dip molding and a dip molded product
US7897979B2 (en) * 2002-06-07 2011-03-01 Semiconductor Energy Laboratory Co., Ltd. Light emitting device and manufacturing method thereof
ITMI20041194A1 (it) * 2004-06-15 2004-09-15 Polimeri Europa Spa Procedimento per la preparazione di lattici a base di policloroprene e loro uso come adesivi
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KR101692099B1 (ko) * 2013-05-24 2017-01-02 주식회사 엘지화학 겔 함량이 낮은 대구경 고무질 중합체 라텍스와 그 제조방법
CN107636032B (zh) 2014-12-12 2020-04-07 昕特玛私人有限公司 用于浸渍成型应用的聚合物乳胶组合物
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WO2001070835A1 (fr) * 2000-03-21 2001-09-27 Basf Aktiengesellschaft Procede de fabrication de particules de caoutchouc
US6723774B2 (en) 2000-03-21 2004-04-20 Basf Aktiengesellschaft Method for producing caoutchouc particles
WO2008034813A1 (fr) * 2006-09-20 2008-03-27 Basf Se Particules contenant un additif polymère
EP2833448B1 (fr) 2012-03-26 2017-11-15 Zeon Corporation Particules composites pour électrodes négatives de batteries secondaires, leur utilisation, leur procédé de production, et composition de liant
US11965046B2 (en) 2016-03-21 2024-04-23 Synthomer Sdn. Bhd. Polymer latex for dip-molding applications
WO2017164726A1 (fr) 2016-03-21 2017-09-28 Synthomer Sdn. Bhd. Latex polymère pour des applications de moulage par immersion
US12359010B2 (en) 2016-03-21 2025-07-15 Synthomer Sdn. Bhd. Polymer latex for dip-molding applications
WO2017209596A1 (fr) 2016-06-01 2017-12-07 Synthomer Sdn. Bhd. Latex polymère destiné aux applications de moulage par immersion
US10982075B2 (en) 2016-06-01 2021-04-20 Synthomer Sdn. Bhd. Polymer latex for dip-molding applications
WO2018111087A1 (fr) 2016-12-15 2018-06-21 Synthomer Sdn. Bhd. Compositions de latex polymère durcissable pour la fabrication d'articles en caoutchouc
US12365153B2 (en) 2019-05-17 2025-07-22 Synthomer Sdn. Bhd. Method for repairing or recycling an elastomeric film
WO2021029763A1 (fr) 2019-08-09 2021-02-18 Synthomer Sdn. Bhd. Composition de latex polymère pour la préparation d'un film élastomère ayant des propriétés autorégénérantes
US12378344B2 (en) 2019-08-09 2025-08-05 Synthomer Sdn. Bhd. Polymer latex composition for the preparation of an elastomeric film having self-healing properties
WO2021054816A1 (fr) 2019-09-20 2021-03-25 Synthomer Sdn. Bhd. Latex polymère pour la préparation d'un film élastomère doté d'excellentes propriétés de rétention de contrainte et d'une excellente souplesse
US12460100B2 (en) 2019-09-20 2025-11-04 Synthomer Sdn. Bhd. Polymer latex for the preparation of an elastomeric film having excellent stress retention properties and softness
WO2021075948A1 (fr) 2019-10-18 2021-04-22 Synthomer Sdn. Bhd. Procédé de production d'un film élastomère continu
US12365773B2 (en) 2019-10-18 2025-07-22 Synthomer Sdn. Bhd. Method for the production of a continuous elastomeric film
WO2021115978A1 (fr) 2019-12-10 2021-06-17 Synthomer Deutschland Gmbh Latex polymère pour une utilisation dans des applications de construction
WO2022010341A1 (fr) 2020-07-07 2022-01-13 Synthomer Sdn Bhd Latex polymère
WO2022216149A1 (fr) 2021-04-07 2022-10-13 Synthomer Sdn Bhd Composition de latex de polymère
WO2023059181A1 (fr) 2021-10-06 2023-04-13 Synthomer Sdn Bhd Latex polymère pour préparer un film élastomère ayant une résistance microbienne
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MX9701507A (es) 1998-06-30
DE19649331A1 (de) 1997-09-04
EP0792891B1 (fr) 1999-08-11
JPH09235306A (ja) 1997-09-09
US5750618A (en) 1998-05-12
CA2198447A1 (fr) 1997-08-29
JP4478217B2 (ja) 2010-06-09
ES2137031T3 (es) 1999-12-01
CA2198447C (fr) 2005-04-19
DE59700321D1 (de) 1999-09-16

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